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Molecular investigation into the transformation of recalcitrant dissolved organic sulfur in refinery sour water during stripping process

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Petroleum Science 2024年第3期21卷 2112-2119页

作者： Yu-Guo Li Chen He Chun-Mao Chen Fan Liu Quan Shi State Key Laboratory of Heavy Oil Processing China University of PetroleumBeijing 102249China State Key Laboratory of Coal Mining and Clean Utilization Beijing 100013China PetroChina Ningxia petrochemical company Yinchuan 750021NingxiaChina

refinery sour water primarily originates from the tops of towers in various units and coker condensate,and cannot be discharged directly to a wastewater treatment plant due to high levels of chemical oxygen demand(COD)and organic sulfur *** after the recovery of H_(2)S from the sour water by the stripping process,the effluent still contains a high concentration of dissolved organic sulfur(DOS),which can have a huge bad *** chemical composition of dissolved organic matter(DOM)in refinery wastewater has been extensively studied,the investigation of recalcitrant DOS from sour waters remains *** the present study,chemical composition of sour water DOMs(especially DOS)was investigated using fluorescence spectroscopy(excitation-emission matrix,EEM)and mass spectrometry,including gas chromatography-mass spectrometry(GC-MS)and high-resolution Orbitrap *** GC-MS and EEM results showed that volatile and low-aromaticity compounds were effectively removed during the stripping process,while compounds with high hydrophilicity and humification degree were found to be more *** Orbitrap MS results showed that weak-polar oxygenated sulfur compounds were easier to be removed than oxygenated ***,the effluent still contained significant amounts of sulfur-containing compounds with multiple sulfur atoms,particularly in the form of highly unsaturated and aromatic *** Orbitrap MS/MS results of CHOS-containing compounds from the effluent indicate that the sulfur atoms may exist as sulfonates,disulfide bonds,*** the composition and structure of sour water DOS is crucial for the development of effective treatment processes that can target polysulfide compounds and minimize their impact on the environment.

关键词： Molecular transformation Dissolved organic sulfur Stripping process refinery sourwater Orbitrap MS

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Catalyst grading technology for promoting the diesel hydrocracking to naphtha

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Petroleum Science 2023年第6期20卷 3798-3806页

作者： Jia-Qi Ge Peng Zhang Fa-Min Sun Ze-An Xie Zhi-Jie Wu Bai-Jun Liu State Key Laboratory of Heavy Oil Processing China University of PetroleumBeijing102249China petrochemical Research Institute PetroChina Company LimitedBeijing102206China daqing petrochemical Research Center PetroChina Company LimitedDaqing163714HeilongjiangChina Institute of Catalysis for Energy and Environment Shenyang Normal UniversityShenyang110034LiaoningChina

This paper reports the application of multi-component hydrocracking catalyst grading technology in diesel hydrocracking system to increase naphtha,and studies the influence of catalyst systems with different number of graded beds on the reaction process of diesel *** hydrocracking catalysts with different physicochemical properties as gradation components,the diesel hydrocracking reaction on catalyst systems of one-component,two-component and three-component graded beds with different loading sequences are carried out and evaluated,*** catalytic mechanism of the multi-component grading system is *** results show that,with the increase of the number of grading beds,the space velocity of reaction on each catalyst increases,which can effectively control the overreaction process;along the flow direction of feedstock,the loading sequences of catalysts with acidity decreasing and pore properties increasing can satisfy the demand of different catalytic activity for the conversion of reactant with changing composition to naphtha,which has a guiding role in the conversion of feedstock to target ***,the conversion of diesel,the selectivity and yield of naphtha all increase significantly on the multi-component catalyst *** research on the grading technology of multi-component catalysts is of great significance to the promotion and application of catalyst systems in various catalytic fields.

关键词： Grading technology Multi-component catalysts Hydrocracking Diesel Naphtha

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Development and Performance Evaluation of Catalyst for Productive Ethylene Cracking Feedstock in Selective Hydrocracking of Straight Run Diesel Oil

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Open Journal of Applied Sciences 2023年第3期13卷 414-423页

作者： Tiezhen Zhang Xin Zhang Yungang Jia Haiyan Li Fangming Xie Zijin Yan Hongyu Tian Hongyu Zhang daqing petrochemical Research Center CNPC Daqing China State Key Laboratory of Heavy Oil Processing China University of Petroleum Beijing China daqing petrochemical company refinery CNPC Daqing China

The upgrading of diesel oil to produce ethylene rich cracking feedstock is an important and promising technical route to reduce the ratio of diesel to gasoline. In the present work, a hydrocracking catalyst suitable for selective hydrocracking of straight run diesel oil to produce high-quality ethylene cracking feedstock at low cost was developed, by optimizing the composition of catalyst support materials, using amorphous silicon aluminum and aluminum oxide with high mesopore content as the main support, and modified Y zeolite with excellent aromatic ring opening selectivity as the acidic component. The catalyst has in-depth characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, N2-low temperature adsorption-desorption, NH3-temperature-programmed desorption, and IR techniques. And its catalytic cracking straight run diesel oil performance was evaluated. The results show that the prepared catalyst has high polycyclic aromatic hydrocarbon ring opening cracking selectivity. However, alkanes retained in diesel distillates can achieve the goal of producing more ethylene cracking feedstocks with low BMCI value under low and moderate pressure conditions. This work may shed significant technical insight for oil refining transformation.

关键词： Straight Run Diesel Mild Hydrocracking Catalyst Ethylene Cracking Feedstock Process Research

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Measurement of pore diffusion factor of porous solid materials

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Petroleum Science 2022年第4期19卷 1897-1904页

作者： Jin-Tao Guo Ya-Qian Wei Sheng-Li Chen Wei Sun Ting-Ting Fan Ming-Ri Xu Chang-Cheng Zhang State Key Laboratory of Heavy Oil Processing and Department of Chemical EngineeringChina University of Petroleum-BeijingBejing102249China petrochemical Research Institute of PetroChina company Limited Daqing163000HeilongjiangChina

Internal diffusion of molecules in porous materials plays an important role in many chemical ***, the pore diffusion capacity of porous materials cannot be measured by conventional catalyst characterization methods. In the present paper, a pore diffusion factor, the ratio of the diffusionconstriction factor to the pore tortuosity of the porous materials, was proposed to measure the diffusion ability of pores inside solid materials, and a method was proposed for measuring the diffusion factor using a well-defined and uniform pore size material as a reference. The diffusion factor was calculated based on the effective diffusion coefficients and the diffusion-constriction factor and pore tortuosity of the reference porous materials. The pore diffusion factor measurement can be performed at room temperature and atmospheric pressure. The pore diffusion factor of conventional porous materials was found to be much smaller than 1, indicating that there is a lot of room for improving the diffusion ability of the conventional catalysts and adsorbents, and could be significantly increased through adding small number of fibers into the conventional porous materials as template.

关键词： Porous materials Well-defined and uniform pore structure materials Internal diffusion Diffusion factor Tortuosity

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Fuzzy optimization design of multicomponent refinery hydrogen network

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Chinese Journal of Chemical Engineering 2022年第8期35卷 125-139页

作者： Chun Deng Xuantong Lu Qixin Zhang Jian Liu Jui-Yuan Lee Xiao Feng State Key Laboratory of Heavy Oil Processing College of Chemical Engineering and EnvironmentChina University of PetroleumBeijing 102249China PetroChina daqing petrochemical company Daqing 163000China Department of Chemical Engineering and Biotechnology National Taipei University of TechnologyTaipei 10608China School of Chemical Engineering&Technology Xi’an Jiaotong UniversityXi’an 710049China

Hydrogen and light hydrocarbon components are essential resources of the *** optimization of the refinery hydrogen system and recovery of the light hydrocarbon components contained in the gas streams are key strategies to reduce the operating costs for sustainable *** research efforts have been focused on the optimization of single impurity hydrogen network,and the flowrates of the hydrogen sources and sinks are assumed to be ***,their flowrates vary along with the quality of crude oil and refinery processing plans.A general superstructure of multicomponent refinery hydrogen network is proposed,which considers four components,namely H_(2),H_(2)S,CH_(4) and C_(2+),as well as the flowrate variations of hydrogen source and hydrogen *** mathematical model based on the superstructure is developed with objective functions,including the minimization of total annualized cost and the maximization of overall satisfaction of the hydrogen ***,the model considers the removal of hydrogen sulfide and the recovery of light hydrocarbon components(i.e.,C_(2+))in the *** verify the applicability of the proposed mathematical model,a simplified industrial case study with four scenarios is *** optimization results show that the economic benefit can be maximized by considering both the direct reuse of gas streams from high-pressure separator(HP gas stream)and from low-pressure separator(LP gas stream)and the recovery of the light hydrocarbon *** fuzzy optimization method can be used to guide the optimal design of the refinery hydrogen system with multi-period variable flowrates.

关键词： Hydrogen network Mathematical programming Multicomponent Fuzzy optimization Light hydrocarbon recovery

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Problems Encountered and Countermeasure Adopted During Processing of Shengli High-sulfur and High-acidity Crude

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China Petroleum Processing & petrochemical Technology 2007年第2期9卷 17-22页

作者： Hu Zhenghai Shengli refinery SINOPEC Qilu Petrochemical Company Zibo 255434

集中的处理高硫、高酸味粗略贡献了精制企业的油的全面经济好处的改进，但是也导致了粗略的乳化，过程单位的严重腐蚀和环境 *** 长周期，过程单位的安全、光滑的操作在最佳的处理线路的选择和一系列技术措施的采纳以后被保证。

关键词：硫磺酸度腐蚀乳化

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Synthesis of Nano-ZSM-5 in Ultra-Concentrated System and Its Performance in Diesel Hydrodewaxing

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China Petroleum Processing & petrochemical Technology 2016年第4期18卷 25-31页

作者： Qin Lihong Li Haiyan Li Jun Sun Famin china university of petroleum Beijing102249 daqing chemical research center petrochemical research institutepetrochina company limitedDaqing163714 daqing petrochemical company construction company petrochina company limitedDaqing163714

Nanocrystalline ZSM-5(with a crystal size in the range of 20—30 nm) has been synthesized in only 20 h via the crystallization of ultra-concentrated homogeneous synthesis mixtures. The influence of low water content, use of compound surfactant, a proper crystallization time and SiO_2/Al_2O_3 molar ratio on the properties of the final nanocrystalline ZSM-5 has been studied. Especially, the use of compound surfactant has influenced some properties of nano-ZSM such as the morphology, crystal size and crystallization greatly. The nano-ZSM-5 zeolite was investigated using XRD, BET, SEM, NH_3-TPD, and other techniques. The evaluation results in a 200-mL hydrogenation unit indicated that the synthesized nano-ZSM-5 had excellent catalytic performance in diesel hydrodewaxing.

关键词：纳米ZSM-5沸石浓缩系统临氢降凝纳米晶合成降凝性能柴油复合表面活性剂

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Commercial Application of RN-10 Catalyst in Coker Gasoline Hydrotreating Unit

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China Petroleum Processing & petrochemical Technology 2000年第4期2卷 48-53页

作者： Wang Futao refinery of daqing petrochemical company Daqing 163711

Since April 1998 the coker gasoline hydrotreating unit at daqing refinery has been using the domestic advanced hydrotreating catalyst RN-10. In the past 1.5 years the RN-10 catalyst has given remarkable high-quality naphtha as did the two batches of RN-1 catalyst during the eight-year period. With the same feedstock and at the same process regime, the RN-10 catalyst has shown its specifics featuring a lower initial reaction temperature, a lower rate of temperature rise, a lower mean reaction temperature, and higher operating flexibility. When processing shoddy gasoline or diesel fuel to produce the same product at identical process operating conditions, the capacity of unit using the RN-10 catalyst can be greatly increased.

关键词： gasoline hydrotreating unit catalyst

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Synthesis and characterization of lower generation broom molecules

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Chinese Chemical Letters 2008年第1期19卷 43-46页

作者： Jun Wang Cui Qin Li Shu Yan Zhang Fang Sun Teng Jie Ge College of Chemistry and Chemical Engineering Daqing Petroleum Institute Daqing 163318 China Fine Chemical Laboratory Research Institute of Daqing Petrochemical Company Daqing 163714 China

Dendritic molecules with dodecyl groups as the hyperbranchs were synthesized in methanol by Michael addition with dodecylamine and methyl acrylate as raw materials. This new-type dendritic molecules were called vividly ＂broom molecules＂ in this report. The surface tension of the aqueous solution of broom molecule terminated amino group was measured by using the dropvolume method. The demulsification performance of the broom molecules for the oil/water （O/W） simulated crude oil emulsion was examined. The experimental results revealed that, as a new-type of surfactants, the broom molecules terminated amino groups showed demulsification for the O/W simulated crude oil emulsion. 2007 Jun Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All fights reserved.

关键词： Dendrimer Broom molecule Surface tension Demulsification

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Measures for Optimization of Aromatic-type and Gasoline-type CCR Technology

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China Petroleum Processing & petrochemical Technology 2006年第3期8卷 1-6页

作者： Bao Wei refinery No. 3 PetroChina Fushun Petrochemical Company Fushun 113001

This article based on the target products manufactured by the gasoline-type and aromatic-type continuous catalytic reforming (CCR) units makes an assessment on the technical indicators of these cata- lytic reforming units. This article also explores the technical measures for maximizing the target products delivered by the gasoline-type and aromatic-type CCR units with respect to the selection of catalysts, the optimization of feedstock and the optimized operating regime.

关键词：芳香族化合物汽油给料催化重整最优化

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